Process for flameproofing treatment

ABSTRACT

A PROCESS FOR FLAMEPROOF TREATMENT OF FIBERS, FILMS, SHEETS, BOARDS AND OTHER ARTICLES BY USE OF A COMPOUND HAVING A GENERAL FORMULA:   R-(S-C(=N+(-R1)-R2)-N(-R3)-R4)N . N/M A(-)   WHEREIN R REPRESENTS A NON-SUBSTITUTED OR SUBSTITUTED HYDROCARBON GROUP OR A HETEROCYCLIC GROUP; AND R1, R2, R3, AND R4, RESPECTIVELY, REPRESENT HYDROGEN ATOM OR NONSUBSTITUTED OR SUBSTITUTED HYDROCARBONS OR A COMPONENT OF A HETEROCYCLIC GROUP FORMED FROM TWO COMPONENTS SELECTED FROM R1, R2, R3, AND R4 AND A REPRESENTS AN INORGANIC OR AN ORGANIC ANION, AND N REPRESENTS AN INTEGER OF 1-6 AND M REPRESENTS THE VALENCY OF A.

United States Patent ABSTRACT OF THE DISCLOSURE A process for flameproof treatment of fibers, films, sheets, boards and other articles by use of a compound having the general formula:

wherein R represents a non-substituted or substituted hydrocarbon group or a heterocyclic group; and R R R and R respectively, represent hydrogen atoms or nonsubstituted or substituted hydrocarbons or a component of a heterocyclic group formed from two components selected from R R R and R and A represents an inorganic or an organic anion, and n represents an integer of 1-6 and m represents the valency of A.

BACKGROUND OF THE INVENTION Field of the invention The present invention relates to a process for flameproofing fibers, films, sheets, boards, and other articles,

. and especially a process for providing permanent flameproofing properties to fibers, films, sheets, boards, and other articles.

Description of the prior art SUMMARY OF THE INVENTION It is an object of the present invention to provide flameproofing agents and retardants for fibers, films, sheets, boards, and other articles, and especially for synthetic fibers for various mixed spun synthetic fibers with cellulose fibers and for various mixed woven or non-woven fabrics.

It is another object of the present invention to provide new types of fiameproofing agents and flame retardants which are useful for rnoquettes.

It is a further object of the present invention to provide a process for flame-proofing fibers, films, sheets, boards, and other articles.

These and other objects have now herein been provided by treating fibres, films, sheets, boards, and other articles with compounds having the general formula:

3,721,581 Patented Mar. 20, 1973 wherein R represents a non-substituted or substituted hydrocarbon group or a heterocyclic group; and R R R and R respectively, represent hydrogen atoms or nonsubstituted or substituted hydrocarbons or a component of a heterocyclic group formed from two components selected from R R R and R and A represents an inorganic or an organic anion; and n represents an integer of 1-6 and m represents the valency of A.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Typical examples of R in the general Formula I include saturated and unsaturated alkyl radicals, such as methyl, ethyl, propyl, butyl, cyclohexyl, vinyl and alkyl radicals, alkylene radicals, such as methylene, ethylene, and propylene radicals; aralkyl radicals, such as benzyl, aryl radicals, such as phenyl, tolyl and xylyl radicals; and heterocyclic radicals, such as pyridinyl, pyrimidinyl, triazinyl, thiazolyl, imidazolyl, oxazolyl, isoxyazolyl, pyrazolyl, quinonyl and acrydyl. Said alkyl, alkylene, aralkyl, aryl and heterocyclic radicals may be substituted by halogen atom, hydroxy, alkoxy, phenyl, epoxy, acyl, acylamine, acyloxy, amino, imino, carbonyl, carboxyl, carboxylic ester, and phosphor containing, such as phosphoric ester, and phosphorous acid ester. Moreover, R can be a polymeric hydrocarbon group which may be substituted by hydroxy, cyano, carboxyl, carboxylic ester, carbamoyl radical, and halogen atom, such as polyvinylalcohol, polyacrylonitrile, polyacrylic acid, esters of polyacrylic acid, polyacrylamide, polystyrene and polyvinylchloride. Typical examples of R R R and R in said general Formula I include hydrogen atoms, saturated and unsaturated alkyl, alkylene, aralkyl, aryl and heterocyclic radicals, as mentioned above for R.

In the present invention, it is especially preferable to employ compounds having the general formula:

wherein R represents an alkyl group or an alkylene group having 1-5 carbon atoms, which may be substituted by halogen atom, hydroxy, alkoxy, phenyl, epoxy, amino, imino, acyl, acylamino, acyloxy, carboxy, and phosphorous containing radicals, said alkyl group or alkylene group may also be combined with each other through one or more bivalent radicals such as --O-, -NH-, CO, 'COO, or a heterocyclic ring such as triazinyl radical; R' R' R' and R'.;, respectively, represent a hydrogen atom, an alkyl group or alkylene group having l-5 carbon atoms as mentioned above for R or two of said R' R R and R, may be combined with each other to form a heterocyclic ring such as:

The compounds having said general Formula I or I can be produced by various methods. Typical processes for producing said compound is to react a compound having the general formula RX (II) (wherein R is the same as that of the general Formula I; X represents a halogen atom and 1 represents an integer of from 1-6) with thiourea or N-derivatives thereof having said general formula:

R4 (wherein R R R and R are, respectively, the same as those of the general Formula I) in a suitable organic solvent, such as alcohol, at room temperature or higher.

Typical examples of compounds having general formula RX are illustrated as follows:

CHzBt CHzBr Br Br OH CHz-CH-CH Br OH 01 CHg-CHCH1 I OH OH CHr-CH-CH-CH:

OH OH Br Br Brom-owmom,

HO CHaCHzI HO CHQCHCH;

HOCH-CHB1 CH3 CH3 CHBnCHaOH CHgBrCHBrOH CHr-CH-CH:

Br OH Br CH -CH-CH:

Br OH OH CHr-CH-CH-CH: )H Br Br OH CHr-CH-CH-CHg Br OH OH 1'31 2)2 HaOHh 4-chlorocynnoline,

3 ,4-dichlorocynnoline, 3-bromo-4-chlorocynnoline, Z-chloropyrimidine,

4-chloropyrimidine, 2,4-dichloropyrimidine, 2,4,6-trichloropyrimidine, S-bromopyrimidine, S-bromo-2-methylpyrimidine,

5 -bromo-2-rnercaptopyrirnidine, 4-bromo-2-aminopyrimidine, 2,4-dichloro--propyloxy-triazine, 5-bromo-4-amino-6-oxy-2-mercaptopyrimidine, 4,6-dichloro-2-methoxypyrimidine,

4,6 -dichloro-2-aminopyrimidine, 4,6-dichloro-Z-methylmercaptopyrimidine, 6-chloro-2-methylmercaptopyrimidine, 2,4,6-tris-bromoethylamino-triazine, 2,4,6-trichlorotriazine,

2-chloro-4,6-bis (bromoethoxy) triazine, 2,4-dichloro-6-bromoethoxyoxytriazine, 2,4,6-tris-bromoethoxytriazine, 2-chloro-4,6-bis (bromopropyloxy) triazine, 5 -bromouracil, S-chloromethyl-1,4-dimethyluracil, 6-chloropurine,

2,6-dichloro-8-oxypurine, 2,6,8-trichloropurine,

Z-chloroquinazoline.

Typical examples of compounds having the general formula:

The compounds having at least one group of thiuronium salt in the molecule having the general Formula I can be used for fiameproofing fibers, films, sheets, boards and other articles made of natural and artificial materials.

For example, cellulose fibers, such as cotton, viscose rayon, cellulose ester or ether fibers, such as cellulose acetate, natural or synthetic fibers made of wool, silk, polyamide such as nylon, polyester, polyacrylonitrile, polyolefine or copolymers thereof, or blend thereof; and blended fibers and blended woven fabrics can be treated with said compounds to provide permanent flame resistant fibers and textiles. Moreover, films, sheets, boards, and other articles formed from resins of polyvinylchloride, polystyrene, polyolefine, polyamide, polyester, polyacrylonitrile, polyurethane, polycarbonate, phenol resin, urea resin, and melamine resin, can be treated with said compounds to provide permanent flame resistant articles.

It is also possible to blend said compounds with said polymers or monomers prior to molding or spinning. The treatment of said articles with said flameproofing agents, according to the present invention, can be accomplished by dipping, coating, spraying or blending. The flameproofing effect can be increased by heating.

Certain embodiments of the process for the flameproofing treatment of fibers are illustrated as follows:

In a preparation of the flameproofing agent bath, it is convenient to use Water, an organic solvent or mixtures thereof as diluent. Since said flameproofing agents are water-soluble, it is preferable to make a bath by dissolving or dispersing said flameproofing agent in an aqueous medium and to continuously or in a batchwise manner dip or apply'said bath to a fabric at from room temperature to C. The fabric treated by said step can be dried and heated at about 100-150 C. It is possible to treat the fabric with various conventional agents for fiber treatment during or following treatment with the flameproofing agents of the present invention to provide more effective flameproofing and to increase durability. Such conventional agents include formaldehyde, methylolurea, methylolthiourea, methylolmelamine, methylolethyleneurea and tetramethylolphosphonium chloride.

The flameproofing agents of the present invention can be used together with conventional flameproofing agents and retardants such as various organic phosphoric acid, organic phosphorous acid, organic phosphonic acid, organic phosphinic acid, organic phosphonous acid, organic phosphine, organic phosphine-oxide; rhodan compounds, e.g., potassium rhodanate, ammonium rhodanate; antimony oxide, titanium tetrachloride, zinc chloride, boric acid and borax.

The flarneproofing agents of the present invention are soluble in an aqueous medium and can provide excellent flameproofing properties to all types of fibers by simple operation. Most conventional flameproofing agents can be applied only to a limited variety of fibers.

For example, conventional agents such as tetrahydroxymethyl phosphonium chloride and tris-azilinine phosphine oxide are effective for cellulose fibers; however, they are ineffective for synthetic polymers, such as polyesters and polyamides. On the other hand, thiourea is slightly effective for polyamides but is ineffective for polyesters or cellulose.

It is one of the advantages of the flameproofing agents of the present invention to impart excellent flameproofing properties to various types of materials such as cellulose, cellulose esters, cellulose ethers, polyesters, polyamides and other natural and synthetic polymers.

Having generally described the invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting in any manner.

In the following examples, the flameproofing test was made by the following method corresponding to JISL- 1079-1966.

(1) Test piece A test piece having 50 mm. of Width and 250 mm. of length is held at 21:1 C., relative humidity 65:2% for 4 hours and then the test is made.

(2) Test method The side of the test piece is held in a horizontal direction so that the longitude of the test piece is in the vertical direction.

A Bunsen burner having 9.5 mm. of inner diameter and 34 mm. of flame length is positioned, keeping 19 mm. of distance between the lower edge of the test piece and the upper edge of the Bunsen burner, and the flame is contacted to the test piece for 12 sec.

After contacting the flame, the Bunsen burner is removed to measure flame time (After flame), glow time 11 (After glow), and length of carbonized portion (melted portion in the case of synthetic fibers) (cm.).

It is preferable that the After flame time and the After glow time be as short as possible and that the length of carbonization or melted portion be less than 12 cm. in length.

EXAMPLE 1 1 mole of a compound having the formula:

TABLE 1 Treated After 10 times washing F G, O, F, G, C, Type of textile see. sec. em. sec. sec. cm.

Cotton 0 4. 8 0 0 5. 9 Polyesterzcotto 0 0 6. 8 0 0 8. 0 Nylon 0 0 7. 5 0 0 8. 6 Polyester 0 0 7. 2 0 0 8. 2

NOTE: In the table, the following abbreviations are used: Polyester: poly-ethyleneterephthalate; F=after flame; G=after glow; C=length of carbonized portion.

EXAMPLE 2 In an aqueous solution containing of a compound having the formula:

NH2 02115-8-0 I BIG and 7% of trimethylolmelamine, the following test pieces of textiles were, respectively, dipped and mangled at the rate of 80% pick up. They were dried and heated for 3 minutes at 140 C. to provide permanent flame resistant textiles. The results of flameproofing tests of textiles treated are shown in Table 2.

TABLE 2 Treated After 10 times washing F, G, C, F, G, C, Type of textile sec. sec. cm. sec. sec. em

0 0 4. 0 0 0 4. 9 0 0 6. 0 0 0 7. 3 0 0 7. 5 0 0 8. 8 Polyester 0 0 7. 1 0 0 8. 0

The treatment was applied to propylene textile, except that the treated textile was heated at 110 C. for 5 minutes. Moreover, the same treatment was used for polyacrylonitrile textiles, except that the treated textile was steamed for 5 minutes with super-saturated steam. The following results of flameproofing tests were found:

Methoxymethyl-thiourea was reacted with excess methyliodide in dimethylformamide at room temperature for 24 hours to obtain a product containing the flameproofing agent having the formula:

or-r o on21 u1-o=Nrn e -I SOH3 as the main product.

In 20% aqueous solution of said product, the following test pieces of textiles were, respectively, dipped and mangled at the rate of pick up. They were dried and heated at C. for 5 minutes to provide permanent flame resistant textiles.

The results of the flameproofing tests are shown in Table 4:

TABLE 4 Treated After 10 times washing F, G, c, F, G, 0, Type of textile see. sec. cm. sec. sec. em.

Cotton 0 0 5 4 0 0 6. 8 Polyester:cotton 0 O 6 1 0 0 7. 2 N on 0 0 6 8 0 0 7. 7 Polyester fiber 0 0 7 5 0 0 8. 4

EXAMPLE 4 65 /NH: OHCH-S-O 01 H3 N Hz G5 NHz CzH50CH-SC o1 CH3 N Hz 6B /NH2 O2H5OCHz-S -o .01

N Hz

The following test pieces of textiles were, respectively, dipped and mangled into a 10% aqueous solution of each compound, at the rate of 100% pick up. They were dried and heated at C. for 3 minutes to provide permanent flame resistant textiles.

The compound (a) was produced by reacting oc-ChlOIO- ethyl alcohol with thiourea, and the compound (-b) was produced by reacting ot-chloroethyl alcohol with thiourea or by introducing hydrochloride gas into the dispersion of acetoaldehyde and thiourea in ethanol, and the compound (c) was produced by reacting ethylchloromethylether with thiourea.

The results of the flameproofing tests on compound (a) are shown in Table 5.

1 mole of C H OCH NHCSNH was reacted with excess of methyliodide in butanol at 60-70 C. for 1 hour. Then butanol was distilled in vacuum and the product was washed with benzene to obtain a flameproof= ing agent containing:

as main product.

The same process was repeated, except using C H OCH -NHCSNHCH -OC H A flameproofing agent containing:

TABLE 6 Treated After 10 times washing Type of textile sec. see. em. sec. sec. cm.

Cotton 0 4. 8 0 0 5. 2 Polyestencotton. 0 0 6. 0 O 0 6. 9 Nylon 0 0 7. 0 0 8.8 Polyester. O 0 7. 0 O 6 7. 9

EXAMPLE 6 Into a aqueous solution of methylol pseudothiourea,

hydrobromide aqueous solution cooled with ice was added dropwise while stirring so that no gel was formed.

The same reaction was carried out using:

N--CH2OCH3 Into said solution, the following test pieces of textiles were, respectively, dipped and mangled at the rate of 80% pick up. They were steamed with super saturated steam for 5 minutes and washed, and dried to provide permanent flame resistant textiles.

EXAMPLE 7 Into an aqueous solution containing of each of the following flameproofing agents and 7% dimethylolthiourea, and 1% accelerator (Sumitex accelerator ACH), the following test pieces of textiles were, respectively, dipped and mangled at the rate of 80% pick up. They were dried at 80 C. for 5 minutes and then heated at 140 C. for 3 minutes to provide permanent flame resistant textiles.

The compound (a) was produced by reacting thiourea with methylene diiodide.

The compound (b) was produced by reacting methylene dithiourea with methyl iodide in methanol.

The results of flameproofing tests of textiles treated with compound (b) are shown in Table 7:

TABLE 7 Treated After 10 times washing F, G, C, F, G, C Type of textile sec. sec. cm. sec. sec. cm.

Cotton 0 0 4s 5 0 0 5. 2 Polyesterzeotton 0 0 6. 7 0 O 7. 8 Nylon 0 0 7. 9 0 0 9. 0 Polyester 0 0 7. 3 0 0 8. 0

The same treatment was used for polypropylene textiles, except that heat was applied at 110 C. for 5 minutes. Moreover, the same treatment was applied to polyacrylonitrile textiles, except that supersaturated steam was applied for 5 minutes.

The following results of the flameproofing tests are found:

TABLE 8 Treated After 10 times washing F, G, c, F, G, 0, Type of textile sec. sec. cm. sec. sec. cm.

Polyaerylonitrile 0 0 5. 1 0 0 6. 7 Polypropylene 0 0 7. 8 0 0 9. 2

EXAMPLE 8 The following textile test pieces were, respectively, treated with dimethylolpseudothiourea having the general formula:

ea Nnomon nocm-s-o -Br The resultant test pieces were, respectively, dipped in a 5% aqueous solution of hydrobromic acid for 5 hours and were mangled at the rate of pickup. They were dried at 80 C. and washed with water, and then were steamed for 5 minutes with super saturated steam to provide excellent permanent flame resistant textiles as shown in Table 9. It is considered that the hydrobromic acid is bonded to the resin made of dimethylolpseudothiourea on the fiber, in the form of thiuronium salt.

TABLE 9 Treated After 10 times washing G, C, Type of textile sec. see. cm. sec. sec. cm

EXAMPLE 9 1 mol of ethylenedibromide and 2 mols of ethylenethiourea were refluxed in ethanol for 10 hours to provide the following compound:

40% formalin solution containing 1 mol of said bisthiuronium salt and 4 mol. of formaldehyde was stirred at room temperature, and then was heated at 50-60 C. and stirred for 5 hours. The resultant methylol compound was diluted with water to prepare the treating bath having 15% solid component.

The following textile test pieces were, respectively, dipped and mangled at the rate of pick up. They were dried and heated at C. for 5 minutes to provide permanent flame resistant textiles. When polyacrylonitrile fiber was tested, the dried test piece was steamed with super saturated steam for 5 minutes. On the other hand, when polypropylene fiber was tested, the dried test pieces was heated at 100 C. for 5 minutes.

The results of flameproofing tests are shown in Table 10:

After 3 times drycleaning TABLE 10 After 10 times Treated washing see.

see.

sec.

sec.

see.

sec.

Type of textiles 092555831539 5 4 O Z3 .5 4&5 5 55 inalzentnt n C0tt0n Polyester:cotton Nylon:rayon Polyacrylzwool.

After 3 times drycleaning F, G, sec. see.

After times washing see. see.

thiouronium salt and 6 mol of formaldehyde was stirred at room temperature, and then was heated at 50-60 C. for 5 hours, under stirring. The resultant compounds were diluted after adding 0.2 mol of guandiyl phosphate to prepare the treating bath having 20% solid component. The following test pieces of textiles were, respectively, dipped and mangled at the rate of 100% pick up. They in the Example 9. The results of flameproofing tests are shown in Table 12:

TABLE 12 Treated F G S60- S00- formalin solution containing 1 mol of said bis- 5 were, respectively, heat treated by the same method shown EXAMPLE 10 1 mol of ethylenedibromdie and 2 mol of thiourea were refluxed in ethanol for 10 hours to provide the following compound:

Type of textiles ea NH:

/CS-CHz-CH2SC N 2 40% formalin solution containing 1 mol of said bis- 2 Polypropylene...

thiuronium salt and 6 mol of formaldehyde was stirred at room temperature, and then was heated at 60 C.

550612059205 A man 35 06 450 082827382909 .o 4-5 23 5 5 fiw5 5 5 5 EXAMPLE 12 1 mol of benzylchloride and 1 mol of N,N'-dimethylthiourea were refluxed in ethanol for 10 hours to provide the following compound:

NH-GHa om-s-o 01 NH-CH3 After 3 times dryeleaning F, G, C 580. S80. cm.

After 10 times washing F, G, sec. sec.

TABLE 11 Treated F, G, sec. sec.

The following test pieces of textiles were, respectively, dipped and mangled at the rate of 100% pick up. They The results of flameproofing tests are shown in Table 11:

for 5 hours. The resulting compounds were diluted with 45 water to prepare the treating bath having 15% solid component.

were, respectively, heat treated by the same method shown 50 in the Example 9.

Type of textiles 7012803 4: .5 5 6 &5

olypropylene... Polyesterzcottonurn EXAMPLE 11 40% Formalin solution containing 1 mol of said thiouro- 1 mol of ethylenedibromide and 2 mol of guanylnium salt and 1 mol of formaldehyde was stirred at room thiourea were refluxed in ethanol for 10 hours to provide temperature and then was heated at 5060 C. for 2 the folowing compound: hours while stirring. The resulting compounds Were diluted to prepare a treating bath of 15% solid component. NH: NHZ The following test pieces of textiles were, respectively, dipped and mangled at the rate of 100% pick up. Thea g; were, respectively, heat treated by the same metho FF NH E NHZ'ZBI shown in the Example 9. The results of flameproofing H H tests are shown in Table 13:

After 13 times dryeleaning F, G, cm. see. sec.

TABLE 13 Treated F, G, C, see. see. cm.

Type of textiles TABLE 15 Treated F, sec. 0, cm.

BrCHzCHCHzO-P ON8 PCH2CO0Na 41 ClCHzCHzO (13) Zinc borate (d) The results of fiameproofing tests are shown in Table 45 16:

TABLE 16 After Treated times washing EXAMPLE CICHzCHzO thiuronium salt or by partially reacting propyl-tribromide with thiourea. The results of the flameproofing tests of textiles treated by the former compound are shown in Table 15:

Type of fiber Cotton Polyester:c0tton Each textile treated in Example 9 was dipped in an aqueous solution containing 7% of each following compound and mangled at the rate of 80% pick up. Each piece was dried and heated at 130 C. for 5 minutes and further was washed and dried to provide permanent flame resistant textiles.

Ammonium salt of polyvinylalcohol phosphate (0) EXAMPLE 13 10 This compound was produced by brominating allyl- The following textile test pieces were, respectively, dipped in each of 8% aqueous solution of:

CH2-CH2-SO4N3 S02\ '15 C Hz- CH2S OiNB /C2H4SQ4N8 S C2H4SO4NB CrH4SO4Na (b) 20 BrCH-COONa BrJJH-COONa (0) Each test piece was mangled at the rate of 80% pick up and dried at 6070 C.

Each sample piece was dipped in 20% aqueous solution of:

oH2s-o The results of the flameproofing tests are shown in Table 14:

TABLE 14 Treated After 10 times washing Treated compound was dried and heated at 130 C. Each piece treated Was 40 washed and dried to provide permanent flame resistant textile.

Each piece was mangled at the rate of 80% pick up and Type of textile EXAMPLE l7 Into an aqueous solution of 15% of the following thiuronium compound, 15% tetrahydroxymethyl phosphonium chloride and 3% triethanolamine, the following 70 test pieces of textiles were dipped and mangled at the The thiuronium compound was produced by reacting 1 75 mole of tris-(propyl dibromo) phosphate with 3 moles of Rayon" Polyester: cotton- Cotton-.

Rayon....- Polyestenc rate of pick up. They were dried at C. for 4.5 minutes and heated at 140 C. for 4.5 minutes to provide permanent flame resistant textiles.

dried and heated at C. for 5 minutes to provide a permanent flame resistant textile.

thiourea. The resulting flameproofing tests are shown in Table 17:

TABLE 17 Treated After 10 times washing F, G, 0, F, G, C, Type of fiber sec. see. em. sec. see. cm.

0 5. 1 0 0 6. 0 0 0 6. 2 0 0 7. 2 N ylon 0 0 6. 8 0 0 7. 6 Polyester- 0 0 7. 2 0 0 8. 0

EXAMPLE 18 Into each aqueous solution of 15% of:

6 NH-CHzOCHa PCHzCI-IzS-C .131

(321150 NH OH2OGH3 and of each of the following compounds, the following test pieces of textiles were, respectively, dipped and mangled at the rate of 80% pick up. They were dried and heated at 130 C. and then were washed and dried to provide permanent flame resistant textiles.

(a) trimethylolrnelamine (b) dimethylolthiourea (c) tetramethylol phosphonium chloride The results of flameproofing tests are shown in Table 18:

TABLE 18 Treated After times washing Type of fiber Agent F, sec. 0,01; F,sec. C, on:

Cotton (a) 0 OOOOOODOOO EXAMPLE 19 Into each aqueous solution of 20% of each following compound, the following test pieces of textiles were, respectively, dipped and mangled at the rate of 80% pick up. They were dried and heated at 130 C. for 5 minutes and then were washed and dried to provide permanent flame resistant textiles.

The compound (a) was produced by reacting CH =CHCONH CH -NH-CSNH which was made of acrylamide, thiourea and formaldehyde, with excess methyl iodide in dimethylformamide at room temperature for one day.

The compound (b) was produced by reacting N- methylol-chloroacetoamide with thiourea.

The compound (0) was produced by condensing 1 mole of cyanurylchloride and 2 moles of ethylene bromohydrine and then reacting 3 moles of thiourea.

The results of flameproo'fing tests are shown in Table following compounds, the following textile test pieces were, respectively, dipped and mangled at the rate of pick up. They were dried and heated at C. for 3 minutes and then were washed and dried to pro Br CHz(|JHCHz-O-(|) C|lO-CH2(|]HCH:B1 .Br

Br N Br (I) /NH2 NHz The results of the fiameproofing tests are shown in Table 20:

TABLE 20 Treated After 10 times washing Type offiber Agent F,sec. C,cm. F,sec. C,cm.

6.1 0.1 8.9 0 6.0 0.1 9.1 0 9.8 0.2 13.0 0 5.3 0 8.0 0 5.3 0 8.0 Polyestenootton- O 6. 4 0 9. 0 Polyester. 0 8. 7 0 12. 4 Cotton 0 6. 5 0.3 10.6 0 6.4 0.3 10.8 0 7.1 0.5 14.1 0 5.9 0.1 9.0 0 5. 8 0.2 9. 7 0 8.0 0.4 14.0

EXAMPLE 21 1 mole of 2,4,6-tris-bromoethyoxy-1,3,5-triazine was dissolved in dimethylformamide, in which dimethylformamide solution of 3 mole of thiourea was added dropwise to react at 90-100 C. for 5 hours. The following compound was obtained:

TABLE 21 After times Treated washing F, G, C, F, G, C, Type of Fiber sec. see. cm. sec sec. cm.

Cotton 0 0 5.5 0 0 6 3 Polyester:c0tt0n 0 0 6.3 0 0 7 5 N 0 0 7.0 0 0 8 0 0 0 7. 1 0 0 8 0 EXAMPLE 22 1 mole of cyanuryl chloride was reacted with 2 moles of allylalcohol in dioxane in the presence of an alkali catalyst, so that 2,4-bis-allyloxy-6-chloro-1,3,5-triazine resulted. The triazine was then brominated to yield:

1 mole of said compound was reacted wtih '3 moles of thiourea to provide an excellent reaction type flameproofing agent. Into an aqueous solution of 15% of said compound, the textile test pieces were, respectively, dipped and mangled at the rate of 70% pick up, and were dried and heated at 140 C. for 3 minutes to provide permanent flame resistant textile. The results of the fiameproofing tests are shown in Table 22:

1 mole of bromoethoxy-trichloro-pyrimidine was reacted with 3 moles of thiourea to yield:

which is a permanent fiameproofing agent.

(hexahydro-triazine derivative) was reacted with thiourea to yield:

which is an excellent permanent flameproofing agent.

EXAMPLE 25 Into an aqueous solution of 1 mole of tetrahydroxymethyl phosphonium chloride shown as an aqueous solution of 4 mole of thiourea was added and stirred at 50 C. for 10 hours. Into this solution, an aqueous solution of ethyl bromide (5 mole) was added and stirred at room temperature for 24 hours. Into the aqueous solution containing a solid component of said product, the textile test pieces were respectively dipped and mangled at the rate of pick up, and then were dried and steamed with super saturated steam for 10 min utes to provide permanent flame resistant textiles. The results of flameproofing tests are shown in Table 23:

TABLE 23 After 10 times Treated washing Type of Fiber sec. sec. cm. sec. sec. cm,

C 0 0 8 0 0 6. 7 Polyester cotton 0 0 6 2 O 0 7.1 Ny n 0 0 6 9 0 0 7. 8 Polyester 0 0 7 0 0 0 7. 8

EXAMPLE 26 Into an aqueous formaldehyde solution having a pH of 8-9 sodium carbonate was added. 1 mole of melamine per 3 moles of formaldehyde was added while stirring to effect a solution at about 60 C. and then was heated at 80-'90 C. to react them, to result transparent syrup of melamine resin. In said syrup, ethyl-pseudo thioureahydrobromate of solid components) was added, and then rayon pulp was mixed and kneaded to impregnate said solution. After kneading the mixture was dried with air at 60-80 C. and crushed into a powder and then a hardener was added.

The melamine resin powder was molded at 135-150 C. under pressure of 105-150 kg./cm. The molding product showed excellent flame resistance in comparison with similar molding products without ethyl-pseudo thiourea hydrobromate.

EXAMPLE 27 1 ground mole of polyvinylalcohol and 1 mole of thiourea were reacted in the presence of 12 moles of 80% H PO at 125 C. for 13 hours to yield a polymer in which about 27% of the hydroxy groups of said polyvinylalcohol are substituted with thiuronium salt.

Into an aqueous solution containing 7% of the thinronium salt of polyvinylalcohol, the following textile test pieces were, respectively, dipped and mangled at the rate of 80% pick up. They were then dried and heated at 130 C. for 5 minutes and were washed with water and dried to provide permanent flame resistant textiles as shown in Table 24:

Having now fully described the invention, it Will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention.

What is claimed as new and desired to be secured by Letters Patent of the United States is:

1. A process for flameproofing fibers, films, sheets, boards or other articles which comprises dipping, coating, spraying or blending said material with a compound having the general formula:

wherein R represents a saturated or unsaturated alkyl radical, an aralkyl radical, an aryl radical, or a heterocyclic radical selected from the group consisting of pyridinyl, pyrimidinyl, triazinyl, thiazolyl, imidazolyl, oxazolyl, isoxyazolyl, pyrazolyl, quinonyl, and acrydyl, which radical may be substituted by ahalogen atom, hydroxy, alkoxy, phenyl, epoxy, acyl, acylamine, acyloxy, amino, imino, carbonyl, carboxyl, carboxylic ester or phosphor, or R is a polymeric hydrocarbon group which may be substituted by hydroxy, cyano, carboxyl, carboxylic ester, carbamoyl radical or halogen atom; and R R R and R4 each respectively, represent a hydrogen atom, or R, or a component of the heterocyclic group formed from two components selected from R R R and R said heterocyclic group being selected from the group consisting of pyridinyl, pyrimidinyl, triazinyl, thiazolyl, imidazolyl, oxazolyl, isoxyazolyl, pyrazolyl, quinonyl, and acrydyl, which group may be substituted by halogen atom, hydroxy, alkoxy, phenyl, epoxy, acyl, acylamine, acyloxy, amino, imino, carbonyl, carboxyl, carboxylic ester, and A represents an inorganic or an organic anion, and n represents an integer of 1 to 4, and m represents the valency of A.

2. The process of claim 1, wherein said material to be fiameproofed is dipped in a solution of said compound, mangled, dried and heated to fix said compound on said material.

3. The process of claim 1, wherein said material treated with said fiameproofing compound is a textile fiber selected from the group consisting of cotton, polyester, nylon, polyacrylonitrile, polypropylene, acetate, vinyl polymer, wool, and polyacryl.

References Cited UNITED STATES PATENTS 2,607,803 8/1952 Lecher 61; a1. 260564 2,910,505 10/1959 Winthrop 260 564 3,535,300 10/1970 Gable 260-29.1

CHARLES E. VAN HORN, Primary Examiner US. Cl. X.R.

252-8.1; 8-1155; 10615 PP; 26()-552 R, Digest 24 

